Triphenylmethane dyes



Patented June 3, 1952 UNITED STATES PATENT OFFICE TRIPHENYLMETHANEv DYES Samuel A. 'Glickman, Easton, I 'Pa., assignor to General Aniline & Film Corporation, New York,

I N. Y., a corporation of Delaware N Drawing.

Application December 16, 1948,

* Serial No. 65,727

8 Claims. 1

The present invention relates to basic triphenylmethane dyestuffs and to a process for preparing them.

I have found new basic triphenylmethane dyestuffs characterized by unusually high solubility in water and alcohol type solvents. These prod ducts are of the general formula:

where n is a small whole number from 2 to 10, where Y is hydrogen, lower alkyl (methyl, ethyl, propyl) halogen (chlorine, bromine), nitro, amino, alkylamino, bis (2 hydroxyethyD- amino, sulfo, carboxyl, carbalkoxy, alkoxy; and where A is an anion of a strong mineral acid such as halide, sulfate, or phosphate or an internal linkage to Y when Y is sulfo or carboxyl. By n averaging from 2 to is meant that this will be the average an the total product which is a mixture wherein some ns may be 1 and others may be, for example, 10 on different molecules or even on the two parts of the same molecule.

The preparation of these dyes involves the condensation of the respectively substituted aromatic aldehyde with the respective N,N-disubstituted aniline containing either one or two omega hydroxypolyoxaalkyl groups followed by oxidation in the usual manner with lead dioxide or manganese dioxide. The condensations are carried out in the presence of hydrochloric or sulphuric acids at temperatures at about 100 C. for several hours. The oxidation takes place p eferably at 0 to 10 C. The following exa ples'serve to illustrate the invention, but they are not intended to limit it thereto.

Example 1 Thirty-five parts by weight of 8,8'-phenyliminobis-3,6-dioxa-l-octanol as obtained by treating aniline with ethylene oxide as described in U. S. Patent 2,161,322, i stirred together-With 6 parts by weight of benzaldehyde and 20 parts by weight of concentrated hydrochloric acid for 24-hours at 100 C. The reaction mixture is diluted with water and the leuco compound, p,p' benzylidene-bislNN bis(8-hydroxy-3,6- dioxaoctyD-aninlinel with the formula given below:

4 [p bis(8 hydroxy- 3,6 -dioxaoctyl) amino-aphenylbenzylidenel 2,5-cyclohexadienylidene- [bis(8 hydroxy-3,6-dioxaoctyl)limonium chloride.

Example 2 i The dye corresponding to the formula:

H(OCHzOHz)a (ongomonn is produced by condensing and oxidizing in the above manner a mixture of 35.0 parts of 8,8

pheny1iminobis-3,6-dioxa-l-octanol, 8.2 parts of para nitrobenzaldehyde and 20 parts of concen ngocmcnm o ain asaviequs v ol t-nil V 3 trated hydrochloric acid. The dye is obtained as a tacky green solid.

Example 3 I 7 The dye corresponding to the formula:

cmomonn mocmcmf wmcmonn is produced by condensing and oxidizing in the" above manner a mixture of 35.0 parts of-8;8"-;

pheny1iminobis-3,6rdioxa-ieoctanol 7.5 partsyby I anisaldehyde and 20.0 a t concentrated hire drochloric acid. The dye is obtained as attack);

is producedlby condensing and oxidizinginthej' above manner a mixture of 35.0 parts of 8,8-

r Enameled: I r "l rue-dy co respondin with the f rmu e- Tlgw isr v antennae moomcnfi V p a 2,598,6(30

nheny minobisrt.tainted-enterin ,-9. par s of a (cuter-150m;

produced a manner similar to theabove by the condensation andio xidation of the mixture from 60 'parts of 17 ,17 phenyliminobis- 3,6,., 2,l,5:mntaoxa l h p edecan Parts Of benzaldehyde; and, 2Q parts at concentrated. hy'

dro c hloric acid.1 The dye, is obtained as a viscous green oil, which isrcompletelymiscible with I water, methanol and ethanol. i

Em n ef" Theidyie corresponding with the formula: mocmcnm (CHzCHzOMHZ V V \i -f a Z cnzomo un issproduced by condensing we; oxidizing in the V L abovamanner a mixture- 61 351W par-ts of 8,8-

'phenyliminobi'sefigfi qdioxa- 1- -octanol; 727 parts 7N Methyl: N

of para. chlorobenzaldehyde and 20.0 parts of concentrated hydrochloric acid. The dye is obtained as a viscous green liquid.

Examples of aromatic aldehydes which may r be reacted with N,N-disubstituted aniline containing either one or two omega'hydroxypoly-V oxaalkyl groups includes the following:

Benzaldehyde Vanillin o, m, or-p-Tolualdehyde p filyaneben zaldehyde c 7 o,:m, or p-chlorobenzaldehyde p-Hydroxybenzaldehyde m-Nitrobenzaldehyde p,-Nitrobenzaldehyde V m=sulfobenzaldehyde mm; or p-Sulfobenzaldehyde i .o'jior pefilarboxybenzaldehyde p-.-Anisa1dehyde m-Sulio, Anisaldehyde 'Piperonal p-Diethylaminobenzaldehyde Examples of tertiary aromatic amines which may be employed are:

(11-hydroxy-3,6,9-trioxaonadecyl) aniline r heptadecyllani-line 14-,1.4' Phenyliminobis. era- 9,12 tetraoxa- 1- tetradecanol The above amines may be obtained from aniline and Nealkylanilines on treatment with ethylene oxide as described in UJS. P. 2,161,322

The compounds so obtained are undoubtedly-a 7 mixture whose average composition is given 'above and are employed as such in' the prepara- 'tion of these noveldyes. v

It will, be? understood that the polyoxyethylene groups-j may-- not. be equally distributed on the two nitrogen atoms of the two aniline molecules but the total; number should; fall within-the averageof: 2 to 10 for each ofhthe anilino groups. 7

Dyes. of; the present invention .when .3? is at tached metaor, para are. suitableafort the manufacture or filterlayers, and: 'antiehalation layers" for. photographic; purposes; In, this, use they possess the advantage over. conventional dyes in that they'may bee employedr inboth, gelatin and alkali-'solublei-resin layersvbyvirtue. of: their; high solubility: of water; and. alcohol type solvents.

Further, these dyes arereadily and completely decolorizedby] alkaline; photographic, developers and are readily-v removed. from photo raphiclayers, containing the'decolorized material. 7 7

A' number of, these'dyes are viscous oils, miscible with, water and glycerin, and are useful in the formulation, of printing inks and pastes In thisconnection the advantageouswaxy viscous nonflzrystalline nature; of z the dyes; i attributed to the polyoxyethyleneu chains The dyessare colored: green and; violet. in acid, and neutral solution' depending on the; number. of chromophoric. g'roupsfl greeni ior two para-substituted chromophoresm and violet for three. paraesulistituted chromophores. 7

By virtue of their solubilityin organic solvents dyesrof; the: above classificationaare -useful thejdyeing oiplastics; andmtherormulationz of lacquers; They:- are useful as: throwsteir' dyes (bl nheblei yec transitory" marking). in: the

fieldgoftextilesz They; may: alsozbeaemployedzin a other. situations where fugitiveidyes are required. Thus they function as: indicators and arecolor less in alkaline solutions (above pH 9) and colored in acid-neutral media.

What I claim is:

1. A new composition of matter comprising wherein n is a small Whole number from 2 to 10, wherein Y is selected from the group consisting of hydrogen, lower alkyl, halogen, nitro, aminoalkyl, amino bis-2 hydroxy ethyl amino, sulfo, carboxyl, carbalkoxy and alkoxy, and where A is an anion of a strong mineral acid.

2. A new composition of matter comprising H(OCH CH (CHzCH)nH wherein 1L is a small whole number from 2 to 6, wherein Y is selected from the group consisting of hydrogen, lower alkyl, halogen, nitro, aminoalkyl, amino bis-2 hydroxy ethyl amino, sulfo, carboxyl, carbalkoxy and alkoxy.

3. A new composition of matter having the following formula:

4. A new composition of matter having the folowing formula:

H(OCH1CH1)3 )CHQCEDOMH moomcm l omomom 5. A new composition of matter having the following formula:

6. A new composition of matter comprising the leuco form of the dyestuff of claim 1.

'7 A new composition of matter having the following formula:

8. A new composition of matter having the following formula:

40 SAMUEL A. GLICKMAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,149,575 Gartner et al Aug. 10, 1915 1,898,523 Boger et al. Feb. 21, 1933 2,091,463 Wolff et al. Aug. 31, 1937 2,161,322 Steindorfi et al. June 6, 1939 

1. A NEW COMPOSITION OF MATTER COMPRISING 